Coated non-metallic sheet having a brushed metal appearance, and coatings for and method of making same

ABSTRACT

A method of making an article that exhibits a metallic appearance includes treating a surface of a non-metallic substrate, e.g. a glass sheet to have a textured surface, and applying an overlay, e.g. a coating over the pattern. The percent of visible light transmittance, and percent visible light reflectance, of the substrate and the overlay is selected such that the pattern is visible when the article is viewed through one of the surfaces of the substrate or overlay. Also provided is a heatable coating having a low emissivity that can be used as the overlay.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 11/639,003,filed Dec. 14, 2006 to Paul A. Medwick et al., entitled “CoatedNon-Metallic Sheet Having a Brushed Metal Appearance, and Coatings forand Method of Making Same.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a coated non-metallic sheet having a brushedmetal appearance, and coatings for, and method of making, the coatednon-metallic sheet, and more particularly, to a glass sheet having atextured surface, and a coating applied over the textured surface toprovide a coated sheet having a brushed metal appearance.

2. Discussion of the Present Technology

Metal sheets having a textured surface (hereinafter also referred to as“textured metal sheets”) have a striking and eye catching appearancewhich makes them desirable for use as part of the interior and exteriordecor of buildings, in the manufacture of furniture, and in themanufacture of appliances. Although the textured metal sheets haveacceptable appearance, there are drawbacks. For example and not limitingto the discussion, the textured metal sheets are opaque, excluding theiruse for transparent areas where viewing and/or transmitting visiblelight is desired. Another drawback is that the textured metal sheets areexpensive, and still another drawback is that the exposed texturedsurface can be scratched and/or dented detracting from the texturedpattern on the metal surface.

As is appreciated by those skilled in the art, it would be advantages toprovide a coated non-metallic sheet or article having a textured metalappearance without having the drawbacks of the presently availabletextured metal sheets.

SUMMARY OF THE INVENTION

This invention relates to an article having a substrate and an overlay.The substrate has a first major surface and an opposite second majorsurface, the second major surface having a textured surface to providethe second surface of the substrate with a predetermined pattern. Theoverlay has a first surface and an opposite second surface with thefirst surface of the overlay in surface contact with the texturedsurface to conform portions of the first surface of the overlay tocorresponding portions of the predetermined pattern, wherein percentvisible light transmittance, and percent visible light reflectance, ofthe substrate having the overlay is selected such that the predeterminedpattern is visible when the article is viewed through the first surfaceof the substrate, or is visible when the article is viewed through thesecond surface of the overlay.

In one non-limiting embodiment of the invention, the overlay is amagnetically sputtered vacuum deposited transparent coating including anaesthetic reflective layer of one or more metals, metal alloys andmixtures thereof, optionally the coating includes a primer layer overthe aesthetic reflective layer, a dielectric layer over the primer layerand a protective overcoat over the dielectric layer.

In another non-limiting embodiment of the invention, the overlay is aheatable coating having a low emissivity and includes a base layer of avisible light absorbing material over one of the surfaces of thesubstrate, preferably on the second surface of the substrate; a firstdielectric layer over the base layer; a first silver layer over thefirst dielectric layer; a first primer layer over the first silverlayer; a second dielectric layer over the first primer layer; a secondsilver layer over the second dielectric layer; a second primer layerover the second silver film; a third dielectric layer over the secondprimer layer; and a protective overcoat over the dielectric layer. Thecoated article has color coordinates according to the CIE 1976 standardwith illuminant D65 at a 10° observer angle of a*=0.3, b*=4.5, andL*=78, wherein the listed color coordinates can vary by ±10%.

In another non-limiting embodiment of the invention, the overlaycomprises a first sub-layer and a second sub-layer, the first sub-layeris the first surface of the overlay and the first sub-layer having anopposite second surface, the second sub-layer is the opposite secondsurface of the overlay and an opposite first surface with the firstsurface of the second sub-layer in facing relationship to the secondsurface of the first sub-layer. The first surface of the layer has avisible light transmission of greater than 0% and the second sub-layerhas a visible light transmission of 0% and visible light reflectance ofthe first surface of the layer is greater than the visible lightreflectance of the substrate such that the predetermined texturedpattern is visible to the unaided eye through the first surface, and notthrough the second surface, of the substrate.

In still another non-limiting embodiment of the invention, the substrateincludes a first layer and a second layer, the first layer having thefirst major surface of the substrate and an opposite second surface, andthe second layer having the second surface of the substrate and anopposite first surface with the first surface of the second layer infacing relationship to the second surface of the first layer, the secondlayer of the substrate having a visible light transmission of 0% and theoverlay has a visible light transmission of greater than 0% such thatthe predetermined textured pattern is visible with the unaided eyethrough the second major surface of the overlay.

Other embodiments of the article of the invention include the substrateand the overlay each have a visible light transmission of greater than0% and further comprising a transparent sheet and a spacer edge assemblyto maintain the transparent sheet and the second surface of the overlayin facing spaced relationship to one another; the substrate and theoverlay each have a visible light transmission of greater than 0% andfurther comprising a transparent sheet and an interlayer sheet to securethe transparent sheet to the second surface of the overlay, and thetextured surface is selected from a plurality of wiggly lines spacedfrom one another, a plurality of spaced cross hatch areas, a series ofbroken arcs that spiral to a center area, one contiguous bent line thatspirals to a the center area, a concave surface, a plurality of spacedcircular depressions, a plurality of raised surfaces, a plurality ofspaced convex portions, one convex portion, and combinations thereof.

Non-limiting embodiments of the article include articles of manufactureselected from furniture, appliances, windows for commercial andresidential buildings, and a vehicle part; windows for commercial andresidential windows comprising the overlay spaced from and in facingrelationship to a protective sheet and a compartment between the overlayand the protective sheet, and a transparency for a vehicle comprising atransparent protective sheet laminated to the overlay.

The invention further relates to a method of making an article thatexhibits a metallic appearance by treating a surface of a non-metalsubstrate to provide a predetermined pattern on the textured surface ofthe substrate; and applying an overlay over the textured surface of thesubstrate, wherein percent visible light transmittance of the substratehaving the overlay, and percent visible light reflectance of thesubstrate having the overlay is selected such that the predeterminedpattern is visible when the article is viewed through one of outersurfaces of the article.

The invention still further relates to a coating having an aestheticreflective layer of one or more metals, metal alloys and mixturesthereof; a primer layer over the aesthetic reflective layer; adielectric layer over the primer layer and optionally a protectiveovercoat over the dielectric layer. Although not required, the coatingcan be a heatable coating.

In one non-limiting embodiment of the coating, the optically reflectivefilm has a thickness in the range of 1 to 20 nanometers (“nm”); theprimer layer is on the aesthetic reflective layer and has a thickness of1 to 10 nanometers (“nm”); the dielectric film is on the primer layerand has a thickness in the range of 1 to 10 nm and the protectiveovercoat is on the dielectric layer and having a thickness in the rangeof 10 to 500 nm.

Other non-limiting embodiments of the coating include the aestheticreflective layer selected from the group of steel, copper, brass,niobium, aluminum, nichrome, tin, nickel, and chrome, noble metals andmixtures thereof, and the primer film selected from the group oftitanium containing material, a zirconium containing material, analuminum containing material, a nickel containing material, a chromiumcontaining material, a hafnium containing material, a copper containingmaterial, a niobium containing material, a tantalum containing material,a vanadium containing material, an indium containing material, a zinccontaining material, and mixtures thereof; the dielectric layer isselected from the group of oxides of titanium, hafnium, zirconium,niobium, zinc, bismuth, lead, indium, tin, zinc and tin, oxides ofindium-tin alloys, silicon nitrides, silicon aluminum nitrides,oxynitrides, and aluminum nitrides, and the protective layer is an oxideof a mixture of silica and alumina

The invention additionally relates to heatable coating having a lowemissivity, the coating includes a layer of a visible light absorbingmaterial; a first dielectric layer over the layer of the visible lightabsorbing material; a first silver layer over the first dielectriclayer; a first primer layer over the first silver layer; a seconddielectric layer over the first primer layer; a second silver layer overthe second dielectric layer; a second primer layer over the secondsilver film; a third dielectric layer over the second primer layer; andoptionally a protective overcoat over the dielectric layer. The coatinghas color coordinates according to the CIE 1976 standard with illuminantD65 at a 10° observer angle of a*=0.3, b*=4.5, and L*=78, wherein thelisted color coordinates can vary by ±10%.

In other non-limiting embodiments of the coating, the layer of thevisible light absorbing material has a thickness in the range of 2 to 10nanometers (“nm”); the first dielectric layer is on the layer of visiblelight absorbing material and has a thickness in the range of 30 to 50nm; the first silver layer is on the first dielectric layer and has athickness in the range of 10 to 100 nm; the first primer layer is on thefirst silver layer and has a thickness in the range of 1 to 6 nm; thesecond dielectric layer is on the first primer layer and has a thicknessin the range of 30 to 50 nm; the second silver layer is on the seconddielectric layer and has a thickness in the range of 10 to 100 nm; thesecond primer layer is on the second silver layer and has a thickness inthe range of 1 to 6 nm; a third dielectric layer is on the second primerlayer and has a thickness in the range of 30 to 50 nm; and a protectiveovercoat is on the third dielectric layer and has a thickness in therange of 10 to 500 nm; and the visible light absorbing material isselected from the group of titanium nitride, nickel, chrome, andmixtures thereof.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an elevated front view of a brushed metal sheet of the priorart.

FIG. 2 is an isometric view having portions removed for purposes ofclarity of a non-limited embodiment of a coated article of the inventionhaving a brushed metal appearance.

FIG. 3 includes FIGS. 3A-3D, 3F and 3H which are elevated front views ofnon-limiting embodiments of textured surfaces that can be used in thepractice of the invention; FIGS. 3E and 3G are views taken along lines3E of FIG. 3D and lines 3G of FIG. 3G, respectively.

FIG. 4 is a view similar to the view of FIG. 2 showing anothernon-limiting embodiment of a coated article of the invention having abrushed metal appearance.

FIG. 5 is a view similar to the view of FIG. 2 showing still anothernon-limiting embodiment of a coated article of the invention having abrushed metal appearance.

FIG. 6 is a view similar to the view of FIG. 2 showing yet anothernon-limiting embodiment of a coated article of the invention having abrushed metal appearance.

FIG. 7 is a view similar to the view of FIG. 2 showing an additionalnon-limiting embodiment f a coated article of the invention having abrushed metal appearance.

FIG. 8 is an elevated side view partially in cross-section showing awindow unit having a non-limiting embodiment of a coated article of theinvention.

FIG. 9 is an elevated side view of a laminated window unit having anon-limiting embodiment of a coated article of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, spatial or directional terms, such as “inner”, “outer”,“left”, “right”, “up”, “down”, “horizontal”, “vertical”, and the like,relate to the invention as it is shown in the drawing figures. However,it is to be understood that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting. Further, all numbers expressing dimensions, physicalcharacteristics, and so forth, used in the specification and claims areto be understood as being modified in all instances by the term “about”.Accordingly, unless indicated to the contrary, the numerical values setforth in the following specification and claims can vary depending uponthe desired properties sought to be obtained by the present invention.At the very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques. Moreover, all ranges disclosed herein are to be understoodto encompass any and all subranges subsumed therein. For example, astated range of “1 to 10” should be considered to include any and allsubranges between (and inclusive of) the minimum value of 1 and themaximum value of 10; that is, all subranges beginning with a minimumvalue of 1 or more and ending with a maximum value of 10 or less, e.g.,1 to 6.7, or 3.2 to 8.1, or 5.5 to 10. Also, as used herein, the terms“deposited over”, “applied over”, or “provided over” mean deposited,applied, or provided on but not necessarily in surface contact with. Forexample, a material “deposited over” a substrate does not preclude thepresence of one or more other materials of the same or differentcomposition located between the deposited material and the sheet orsubstrate.

Before discussing non-limiting embodiments of the invention, it isunderstood that the invention is not limited in its application to thedetails of the particular non-limiting embodiments shown and discussedherein since the invention is capable of other embodiments. Further, theterminology used herein to discuss the invention is for the purpose ofdescription and is not of limitation. Still further, unless indicatedotherwise in the following discussion, like numbers refer to likeelements.

The use of the coated non-metallic sheet of the invention having atextured metal appearance is not limiting to the invention and can beused to make any article of manufacture including but not limited tofurniture, e.g, but not limited to table tops, counter tops, windows forcabinets and doors; to appliances, e.g. but not limited to oven doors,refrigerator doors, clock faces; to windows for commercial andresidential buildings, and to uses in vehicle applications, e.g. but notlimited to recreational vehicle windows, and automotive roof, side,front and rear windows.

Shown in FIG. 1 is a prior art textured metal sheet or textured metalarticle 20. The textured metal article 20 includes scratches or grooves22 of varying depth, width and length imposed in major surface 24 ofmetal sheet 26 to provide the textured metal appearance to the article20 in accordance to the teachings of the prior art. The metal sheet 26is any metal, e.g. stainless steel, copper or aluminum, and in oneembodiment of the prior art, the metal is stainless steel, and thetextured metal surface 24 is optionally a polished surface or anunpolished surface.

Shown in FIG. 2 is one non-limiting embodiment of a coated texturednon-metallic article of the invention designated by the number 30; thearticle 30 has a textured metal appearance in accordance to theteachings of the invention. More particularly, the coated texturednon-metallic article 30 includes a non-metallic sheet or substrate 32having a first major surface 34 and an opposite second major surface 35.The second major surface 35 has a plurality of raised surface portionsand/or scratches or grooves 37 of varying depth, width, length, heightand/or shape imposed in and/or on the second major surface 35 of thesheet 32 to provide the major surface 35 with a textured appearance. Forease of discussion, the second major surface 35 having the raisedportions and/or grooves 37 is also referred to as “textured surface 38.”A non-limiting embodiment of an overlay or coating 40 of the inventionis applied over the textured surface 38. The article 30 under discussionhas a visible light transmission greater than 0%. As used herein, theterm “visible light” means wavelengths of the electromagnetic spectrumin the range of 380-780 nanometers. However, it should be appreciatedthat other non-limiting embodiments of the invention include a coating40 that has 0% visible light transmission, i.e. the coating is opaque.

The sheet or substrate 32 of the article 30 can be made of any materialthat has a visible light transmission greater than 0%. Materials thatcan be used in the practice of the invention for the sheet 32 include,but are not limited to, any type of plastic that is transparent tovisible light, e.g. and not limited to polymeric materials,polycarbonate, acrylic and polyethylene terephthalate, and any type ofglass that is transparent to visible light, e.g. and not limited toceramic materials, glass-ceramic materials, glass materials e.g. but notlimiting to the invention soda-lime-silicate glass, borosilicate glass,or any type of refractory glass and combinations thereof. The glass andplastic can be clear or tinted, and can be made in any manner.

In a preferred non-limiting embodiment of the invention, the sheet 32 isa glass sheet. Tinted glass sheets can be used in the practice of theinvention and include, but are not limited to the types disclosed inU.S. Pat. Nos. 5,030,592; 5,240,886; 5,593,929, and 5,792,559, thedisclosures of the patents are hereby incorporated by reference. Theglass sheet can be annealed glass, tempered glass, or heat strengthenedglass. In another non-limiting embodiment of the invention, the glass ismade by float glass processes, e.g. but not limited to the float glassprocesses disclosed in U.S. Pat. Nos. 3,083,551; 3,220,816, and3,843,346, which disclosures are hereby incorporated by reference. Inanother non-limiting embodiment of the invention, the sheet 32 is asoda-lime-silicate glass sheet of the type sold by PPG Industries, Inc.under the registered trademark Starphire®.

Still further, the sheet 32 can be a monolithic sheet or a laminate,e.g. two sheets of the same or different materials, e.g. but notlimiting to the invention, glass and plastic joined together by aninterlayer material. In addition, the major surfaces 34 and 35 of thesheet 32 can have one or both major surfaces 34 and 35 flat or curved,or one major surface flat and the other major surface curved, and/or thespaced apart major surfaces 34 and 35 can be parallel to each other orat least a portion of one major surface can be angularly offset from theother major surface.

The discussion is directed to the textured surface 38 of the sheet 32.The term “textured surface” as used herein means that the angle ofincidence of a collimated beam of light impinging and moving over aportion of a textured surface has an angle of reflection different fromthe angle of incidence. The invention is not limited to any particulardesign or predetermined pattern of the textured surface. As used herein,the term “predetermined pattern” is not limited to any particular designand includes both regular and random patterns. In addition, it can beappreciated that the predetermined pattern can include linear and/ornonlinear lines and/or line segments. For example, and not limiting tothe invention, the grooves 37 can be similar in shape and design to thegrooves 22 of the textured metal plate 20 of FIG. 1. For example and notlimiting to the invention, the grooves 37 shown in FIG. 2 can have alength up to 5 centimeters (“cm”), for example up to 1 cm, a widthranging from 1-100 microns, for example from 10-20 microns with thewidth of the grooves varying between ends of the grooves, and a depthranging from 0.05-1 microns, for example from 0.1-0.2 microns, with thedepth varying between the ends of the grooves. Shown in FIG. 3, areother non-limiting embodiments of textured surface that can be used inthe practice of the invention.

With reference to FIG. 3, textured surface 42 of sheet 44 shown in FIG.3A includes a plurality of nonlinear grooves 46 spaced from one another.In the particular non-limiting embodiment shown in FIG. 3, the grooves46 are generally sinusoidal in shape. Textured surface 50 of sheet 52shown in FIG. 3B has a plurality of spaced grooves crossing one anotherto give a cross hatched appearance 54. As can be appreciated, thegrooves can extend to opposite edges of the sheet 52 to cover the totalsurface area of the sheet with one cross hatch pattern as shown in FIG.3B or with a plurality of spaced cross hatched areas (not shown).Textured surface 60 of sheet 62 shown in FIG. 3C is a series of groovesin the shape of broken arcs 64 that spiral to center 68. As can beappreciated the spiral can be one contiguous groove that spirals to thecenter 68. Textured surface 70 of sheet 72 shown in FIGS. 3D and 3E hasone or a plurality of spaced apart depressed, or concave, surfaceportions 74. The depressions can have any shape, e.g. but not limitingto the invention, circular, triangular, square, rectangular orpolyhedral and combinations thereof. Textured surface 80 of sheet 82shown in FIGS. 3F and 3G includes one or a plurality of spaced apartraised, or convex, surface portions 84. The convex portions 84 can haveany shape, e.g. but not limiting to the invention, circular, triangular,square, rectangular or polyhedral and combinations thereof. Texturedsurface 90 of the sheet 92 shown in FIG. 3H is a picture 94 of anobject. The invention is not limited thereto and the picture 94 of thetextured surface 90 can be a picture of a person and/or an object, e.g.,topography of the earth, sky and/or planets. The textured surfaces ofthe invention are not limited to the non-limiting embodiment shown inFIGS. 2 and 3, and the textured surface can be combinations of thetextured surfaces shown in FIGS. 2 and 3, and can be any otherconfiguration.

In another non-limiting embodiment of the invention, the texturedsurface of the invention is a translucent surface, e.g. and not limitingto the invention, the major surface 35 of the sheet 32 can be acidetched or mechanically abraded to be a translucent surface. In anothernon-limiting embodiment of the invention at least 20%, e.g. at least50%, or at least 80%, or at least 90%, of the total surface area of amajor surface, e.g. and not limiting to the invention, the major surface35 of the sheet 32, is textured.

In still another non-limiting embodiment of the invention, the texturedsurface 32 of the uncoated sheet or substrate 32 has a Delta % hazegreater than 0%. The % haze is the % of light passing through the sheet.The haze measurement is made using a TCS spectrophotometer marketed byBYK-Gardner and sold under the mark HAZE-GARD. In use, a light source ispositioned on the side of the sheet opposite to the side of the sheet tobe textured, i.e. the light source is on the side 34 of the sheet 32shown in FIG. 2. As is appreciated by those skilled in the art, thesheet is cleaned and dried before the measurements are taken. The Delta% haze is the difference between the % haze of a sheet prior totexturing the surface of the sheet, and after texturing the surface ofthe sheet.

The raised portions and/or grooves 37 can be imposed on or in thesurface of the sheet, e.g. the surface 35 of the sheet 32, in anyconvenient manner to provide the textured surface 38. In onenon-limiting embodiment of the invention, the scratches are provided bypracticing the prior art process of imposing the scratches 24 in thesurface 22 of the metal sheet 20. More particularly and not limiting tothe invention, the sheet 32 is moved past a rotating cylinder havingabrading material on selected outer surface portions of the cylinder(hereinafter also referred to as “the surface treatment step”). Inanother non-limiting embodiment of the invention, the scratches 37 canbe imposed in the surface 35 by rubbing the substrate 32 with anabrasive slurry (i.e., grit in a liquid carrier) or an abrasive grit(i.e., grit in powder form). Suitable abrasive grits include hardmaterials such as silicon carbide, ceria, alumina, boron carbide anddiamond. Any convenient rubbing process can be utilized. In anon-limiting embodiment of the present invention, the treating stepincludes brushing the sheet or substrate 32, e.g. the brushing can beaccomplished using one or more Scotch-Brite® scouring pads, a pad withsilicon carbide embedded in it, nylon brushes having bristles impingedwith abrasive grits. Any brushing process known in the art can beutilized in the practice of the invention to provide the texturedsurface 38. In still another non-limiting embodiment of the inventionthe surface is textured using a laser or an air abrasive jet. As isappreciated by those skilled in the art, after the treatment step andprior to making the coated article, it is understood that the abradedsheet is cleaned and dried, in any convenient manner.

In another non-limiting embodiment of the invention, the surface 35 ofthe sheet 32 can be textured while the sheet is being manufactured, e.g.and not limiting to the invention, glass can be textured either on-linein the glass float bath, or on-line downstream of the glass float bath.For example, but not limiting to the invention, the glass can betextured using the process disclosed in U.S. Pat. No. 4,746,347, whichincludes passing a glass ribbon while supported on molten metal in thefloat bath forming chamber under a metal roll having a patternedsurface, and in U.S. Patent Application Publication No. 2003/0037569,which includes dropping glass particles on the surface of the glassribbon while in the float bath forming chamber. U.S. Pat. No. 4,746,347and U.S. Patent Application Publication No. 2003/0037569 are herebyincorporated by reference.

The invention is not limited to the material of the coating 40 onsurface 35. In one non-limiting embodiment of the invention, the coating40 is selected to provide the coated article 30 when viewed through thesurface 34 (the surface opposite the textured surface 38) with a percentof visible light reflectance greater than the percent of visible lightreflectance of the sheet 32 when the sheet 32 is viewed through themajor surface 34. The percent of visible light reflectance between thecoated article 30 and the sheet 32 is not limiting to the invention andin one non-limiting embodiment the difference is at least 10 percent,e.g. at least 20 percent, or at least 30 percent, or at least 40percent. The percent of visible light reflectance of the coated articlewhen viewed through surface 90 of the coating 40 of coated article 30 isnot limiting to the invention, and can be equal to, greater than, orless than, the percent of visible light reflectance of the coatedarticle 30 when the coated article is viewed through the uncoatedsurface 34.

In one non-limiting embodiment of the invention, at least a portion ofthe surface area of the raised portions and/or grooves is covered by thecoating 40 so that the surface of the coating 40 contacting the texturedsurface 38 is not planed, i.e. the coating at the coating 40/surface 38interface follows the contours of the textured surface 38. In thismanner, the coating reflects the pattern of the textured surface 38, andthe pattern of the textured surface 38 surface can be seen by viewingthe coated article. In a further non-limiting embodiment, the surface ofcoating 40 opposite surface 38 generally maintains the same texturedsurface profile as textured surface 38 of sheet 32.

In another non-limiting embodiment of the invention, at least a portionof the surface area of the raised portions and/or grooves is covered bythe coating 40 such that coating 40 fills in the textured surface 38 andthe surface of the coating 40 opposite the textured surface 38 presentsa smooth surface. In an arrangement of this type, if the coating 40 istransparent, the article 30 will still exhibit a textured coatingappearance when viewed from either side of the article. In anarrangement of this type where the coating 40 is opaque, e.g. coating 40is a thick metal coating, the article 30 will appear opaque when viewedfrom the coating side and textured when viewed through sheet 32.

The coating 40 alone or in combination with the sheet 32, i.e. thecoated article 30, can have any reflective color or can simulate thecolor of any metal, e.g. but not limiting to the invention to gold,silver, aluminum, stainless steel, copper, brass, niobium, aluminum,nichrome, tin, nickel and chrome. The aesthetic properties of the coatedarticle 30 of the present invention will vary depending on the desiredmetallic appearance. For example, if the desired metallic appearance isthat of steel, the coated article 30 will have different aestheticproperties than if the desired metallic appearance is that of brass.

Ranges for the aesthetic properties of the coated article according tothe present invention are provided below for various metallicappearances. The aesthetic properties of the coated substrate arerepresented by color coordinates according to the CIE 1976 standard withilluminant D65 at a 10° observer angle. The listed color coordinates canvary by ±10% and are not limiting to the invention.

TABLE 1 Aesthetic Properties Exhibited by Coated Substrates according tothe Present Invention Desired Metallic Appearance a* b* L* Buffed copper13.3 14.9 85.6 Dull copper 22.3 29.7 71.3 Brass 3.0 27.6 69.6 Oxidizedbrass 7.5 46.0 55.9 Polished brass 0.4 23.3 84.2 Brushed stainless steel0.3 4.5 78.0 Polished niobium 0.6 2.7 70.1 Aluminum 0.3 3.4 83.6 Dullaluminum 0.8 6.3 79.2 Nichrome 0.5 5.4 77.1 Gold 10.8 35.8 76.2

The coating 40 (see FIG. 2) can be deposited using conventionaldeposition techniques such as chemical vapor deposition (“CVD”), spraypyrolysis, atmospheric plasma deposition and magnetron sputtered vacuumdeposition (“MSVD”) as are well known in the art. Suitable spraypyrolysis methods of deposition are described in the followingreferences which are hereby incorporated by reference: U.S. Pat. Nos.4,719,126; 4,719,127; 4,111,150; and 3,660,061. Suitable MSVD methods ofdeposition are described in the following references which are herebyincorporated by reference: U.S. Pat. Nos. 4,379,040; 4,861,669; and4,900,633. Although not limiting to the invention, unless indicatedother wise, the following non-limiting embodiments of coatings of theinvention are applied using any type of vacuum deposition, e.g. usingMSVD.

In a first non-limiting embodiment of a coating of the invention, thecoating 40 is transparent to visible light, is heatable and has areflective layer or film that passes and reflects visible light(hereinafter also referred to as “an aesthetic reflective layer”). Theterm “transparent to visible light” means the coating has greater than0% transmission of visible light. The term “heatable” means the coatingcan be heated to a temperature above room temperature withoutdeteriorating the layers, e.g. metal layers of the coating. The term“reflects visible light” means that the coating reflects at least somevisible light. Usually for processing glass, the coating has towithstand temperatures equal to or greater than 1000° F. (538° C.), e.g.and not limiting to the invention, temperatures can be equal to orgreater than 1100° F. (593° C.) for glass press bending operations, andtemperatures equal to or greater than 1200° F. (649° C.) for glasstempering operations.

The non-limiting embodiment of the coating, includes an aestheticreflective layer of one or more metals, metal alloys and mixturesthereof, having a thickness in the range of 1 to 20 nanometers (“nm”),e.g. in the range of 5 to 15 nm, provided over, and e.g. in surfacecontact with, the textured surface 38; a primer layer or film having athickness in the range of 1 to 10 nm, e.g. in the range of 2 to 8 nm,provided over, and e.g. in surface contact with, the aestheticreflective layer; a dielectric layer having a thickness in the range of1 to 10 nm, e.g. in the range of 2 to 8 nm, provided over, and e.g. insurface contact with, the primer layer; and a protective overcoat havinga thickness in the range of 10 to 500 nm, e.g. in the range of 50 to 300nm, provided over, and e.g. in surface contact with, the dielectriclayer.

The aesthetic reflective layer of a metal, metal alloy and mixturesthereof provides a surface to reflect visible light so that the coatedarticle has a percent of visible light reflectance greater than thepercent of visible light reflectance of the sheet 32 as discussed above.Suitable metals for the aesthetic reflective layer include, but are notlimited to, steel (for example, grade 316 steel), copper, brass,niobium, aluminum, nichrome, tin, nickel, chrome, and noble metals, suchas silver, gold, copper, platinum, iridium, osmium, and alloys andmixtures thereof. As is appreciated by those skilled in the art, themetal, metal alloy and mixtures that can be used for the aestheticreflective layer also have the property of reflecting infrared energy,providing the above coating of the invention with infrared reflectiveand emissivity properties. Infrared energy is defined as wavelengths ofthe electromagnetic spectrum greater than 780 nm. The term “highemissivity” is defined as an emissivity equal to or greater than 0.3; anemissivity below 0.3 is considered “low emissivity.” The emissivity ofthe coating depends on the metal selected, e.g. a silver film has a lowemissivity, and a steel film has a high emissivity.

As is well known in the art, the primer layer provides protection to theaesthetic reflective layer during heating of the coating and during thedeposition of the dielectric layer practicing MSVD. Suitable primerlayers include oxygen-capturing or oxygen-reactive materials such as,but not limited to, a titanium containing material, a zirconiumcontaining material, an aluminum containing material, a nickelcontaining material, a chromium containing material, a hafniumcontaining material, a copper containing material, a niobium containingmaterial, a tantalum containing material, a vanadium containingmaterial, an indium containing material, and a zinc containing material.

The discussion is now directed to the dielectric layer and theprotective layer of the above coating. When the surface 90 of thecoating 40 of the coated article 30 (see FIG. 2) is exposed, the surface90 should be protected to prevent or reduce deterioration of the coatingfrom cleaning solutions, touching and the atmosphere. As can beappreciated, exposed coated surfaces, in particular MSVD coated primerlayers and films are generally not durable and should be protected by ahard protective coating to prevent or reduce deterioration. In onenon-limiting embodiment of the invention, a protective overcoat of thetype disclosed in U.S. Pat. Nos. 6,869,644 B2; 6,916,542 B2, and6,962,759 B 2, which patents are hereby incorporated by reference, isused. In another non-limiting embodiment of the invention, theprotective coating is a mixture of silica and alumina, e.g.Si_(0.85)Al_(0.15)O_(x). Other non-limiting techniques to protect thecoating 40 against deterioration are discussed below.

A silica and alumina protective overcoat can be used in the practice ofthe invention for MSVD coatings. One of the limitations of theprotective overcoat is that during its deposition by MSVD, it chemicallyattacks metals; therefore, the aesthetic reflective layer and the primerlayer, if present, has to be protected during the deposition of theprotective overcoat. In one non-limiting embodiment of the invention,the aesthetic reflective layer is protected by the primer layer, and theprimer layer is protected by the dielectric film. As can be appreciated,if the silica and alumina protective overcoat is not used in thepractice of the invention and the article 30 is not heated, the coatedarticle 30 need only include the aesthetic reflective layer, and if thesilica and alumina protective overcoat is not used in the practice ofthe invention and the article is heated, the coated article 30 need onlyinclude the aesthetic reflective layer and the primer layer. It shouldbe further appreciated that the primer layer should be applied over thesilver layer in a manner that does not materially affect the propertiesof the silver. For example and not limiting in the present invention,where the primer is titanium, it can be sputter deposited over thesilver in a non-reactive atmosphere and subsequently be converted toTiO₂ by heating the coating or sputter depositing another layer over thetitanium using a reactive atmosphere.

Suitable materials that can be used for a dielectric layer includes butis not limited to metal oxides, oxides of metal alloys, nitrides,oxynitrides, or mixtures thereof. Examples of suitable metal oxidesinclude, but are not limited to, oxides of titanium, hafnium, zirconium,niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof.Additionally, the dielectric layer can include oxides of metal alloys ormetal mixtures, such as, but not limited to, oxides containing zinc andtin, oxides of indium-tin alloys, silicon nitrides, silicon aluminumnitrides, oxynitrides, or aluminum nitrides. For example, the dielectriclayer can include a zinc/tin alloy oxide such as “zinc stannate” whichrefers to a composition of Zn_(x)Sn_(1-x)O_(2-x) (Formula 1) where x isgreater than 0 but less than 1. If x=⅔, for example, the zinc stannateformed would be represented by Zn_(2/3)Sn_(1/3)O_(4/3) which is commonlydescribed as “Zn₂SnO₄”.

In a second non-limiting embodiment of a coating of the invention, thecoating is a transparent, low emissivity, heatable coating having silverfilms that have the appearance of brushed stainless steel (see Table 1above). More particularly, the coated article 30 has the appearance ofbrushed stainless steel and the infrared reflecting properties of asilver coating. The coating of the invention includes a layer of avisible light absorbing material having a thickness in the range of 2 to10 nm, e.g. in the range of 4 to 8 nm, provided over the texturedsurface 38, and e.g. in surface contact with, the textured surface; afirst dielectric layer having a thickness in the range of 30 to 50 nm,e.g. in the range of 37 to 44 nm, provided over, and e.g. in surfacecontact with, the layer of visible light absorbing material; a firstsilver layer having a thickness in the range of 10 to 100 nm, e.g. inthe range of 30 to 100 nm, provided over, and e.g. in surface contactwith, the first dielectric layer; a first primer layer having athickness in the range of 1 to 6 nm, e.g. in the range of 2 to 4 nm,provided over, and e.g. in surface contact with, the first silver layer;a second dielectric layer having a thickness in the range of 30 to 50nm, e.g. in the range of 37 to 44 nm, provided over, and e.g. in surfacecontact with, the first primer layer; a second silver layer having athickness in the range of 10 to 100 nm, e.g. in the range of from 30 to100 nm, provided over, and e.g. in surface contact with the seconddielectric layer; a second primer layer having a thickness in the rangeof 1 to 6 nm, e.g. in the range of 2 to 4 nm, provided over, and e.g. insurface contact with, the second silver; a third dielectric layer havinga thickness in the range of 30 to 50 nm, e.g. in the range of 37 to 44nm, provided over, and e.g. in surface contact with, the second primerlayer; and a protective overcoat having a thickness in the range of 10to 500 nm, e.g. in the range of 50 to 300 nm, provided over, and e.g. insurface contact with, the dielectric layer.

In another non-limiting embodiment of the second coating, the firstsilver layer has a thickness in the range of 5 to 20 nm, e.g. 10 to 15nm; the second silver layer has a thickness in the range of 5 to 15 nm,e.g. 10 to 12 nm; the first and second primer layers each have athickness in the range of 1 to 6 nm, e.g. in the range of 2 to 4 nm; thefirst and second dielectric layers each have a thickness in the range of20 to 40 nm, e.g. in the range of 25 to 35 nm, and the protectiveovercoat has a thickness in the range of 10 to 500 nm, e.g. in the rangeof 50 to 300 nm.

The materials of the primer layers, the dielectric layers, and theprotective overcoat of the second non-limiting coating embodiment can bethe same as the materials of the primer layer, the dielectric layer, andthe protective overcoat of the first non-limiting coating embodimentdescribed above.

The layer of visible light absorbing material between the silver layerand the substrate reduces the percent of visible light reflection of thesilver layers when the coated article is viewed through the uncoatedsurface 34 (see FIG. 2). In this manner, the percent of visible lightreflectance of the silver is greater when the coated article 30 isviewed through the surface 90 of the coated article than when viewedthrough the surface 34 of the coated article to provide the coatedarticle 30 with the color coordinates of brushed stainless steel (seeTable 1). As can now be appreciated, providing the silver layers betweenthe substrate and a layer of visible light absorbing material will havean opposite effect, e.g. the percent of visible light reflectance of thesilver layers is greater when viewed through the surface 34 than whenviewed through the surface 90 of the coated article.

Materials that can be used for visible light absorbing materialsinclude, but are not limited to titanium nitride, nickel and chromeincluding alloys such as nichrome sold under the trademark Inconel®alloy which is commercially available from The Special MetalsCorporation (NY), and mixtures thereof.

In a non-limiting embodiment of the invention, the sheet or substrate 32can be subjected to a heat treatment such as press bending, tempering,etc. The sheet 32 can be subjected to heat treatment after the coating40 is applied over the textured surface 38, or the sheet 32 can besubjected to heat treatment before the coating 40 is applied over thetextured surface 38.

As can be appreciated, the invention is not limited to the coating layer40 and other coatings, e.g. the coatings disclosed in U.S. Pat. Nos.4,806,220; 4,853,256 and 4,898,789, which disclosures are herebyincorporated by reference.

Another non-limiting embodiment of a coated article of the invention isshown in FIG. 4 and is designed by the number 142. The coated article142 includes the sheet or substrate 32 having the textured surface 38and an opaque layer 144 having 0% visible light transmission and havinga reflective surface 145. The reflective surface 145 is over and securedto the textured surface 38, with portions of the reflective surface inthe grooves of the textured surface. The percent visible lightreflection of the surface 145 of the layer 144 is greater than thepercent of visible light reflection of the sheet 32, to view thetextured surface 38 through the surface 34.

The invention is not limited to the materials of the opaque layer 144;however, the reflective surface 145 of the opaque layer preferablyconforms to the textured surface 38 as discussed above so that thetextured surface is visibly observable from the uncoated surface 34 ofthe coated article 142. Materials for the opaque layer 144 that can beused in the practice of the invention include, but are not limited to,thick MSVD coating layers of metal, metal oxides and mixtures thereof,e.g. but not limiting the invention thereto, steel (for example, grade316 steel), copper, brass, niobium, aluminum, nichrome, tin, nickel andchrome, titanium containing material, zirconium containing material, analuminum containing material, a nickel containing material, a chromiumcontaining material, a hafnium containing material, a copper containingmaterial, a niobium containing material, a tantalum containing material,a vanadium containing material, an indium containing material. Thethickness of the coated layer 144 is not limited to the invention, buthas a minimum coating thickness for the coating layer 144 to have avisible light transmission of 0%.

In the instance when the opaque layer 144 is applied as a liquidcoating, it can be applied in any conventional manner, e.g. by spraying,dip coating and brush application. In the instance when the opaque layer144 is applied as a vapor or by vacuum deposition, any of the coatingmethods discussed above for applying the coating 40 of the coatedarticle 30 of FIG. 2 can be used. In another non-limiting embodiment ofthe invention, when the opaque layer 144 is applied as a solid, e.g. thelayer 144 is a metal foil; the metal foil is applied to the texturedsurface, e.g. by moving a roller having a pliable body over the layer,biasing the layer against the textured surface, or by using positive ornegative fluid pressure, e.g. air pressure to the bias the metal foillayer against the textured surface. Optionally and not limiting to theinvention, the layer 144 of metal foil can be secured against thetextured surface 38 by a thin layer of adhesive transparent to visiblelight.

In a non-limiting embodiment, the opaque layer 144 is an opaque, visiblelight reflective, coating comprising the following: a layer of one ormore metals, metal alloys and mixtures thereof, e.g. and not limiting tothe invention having a thickness in the range of 10 to 100 nm, e.g. from30 to 100 nm, provided over, and e.g. in surface contact with, thetextured surface 38; a primer layer having a thickness in the range of 1to 6 nm, e.g. in the range of 2 to 4 nm, provided over, and e.g. insurface contact with, the layer of one or more metals, metal alloys andmixtures thereof; a dielectric layer having a thickness in the range of1 to 10 nm, e.g. in the range of 2 to 8 nm, provided over, and e.g. insurface contact with, the primer layer; and a protective overcoat havinga thickness in the range of 10 to 500 nm, e.g. in the range of 20 to 300nm, provided over, and e.g. in surface contact with, the dielectriclayer.

The layer of one or more metals, metal alloys and mixtures thereof, theprimer layer, the dielectric layer and the protective overcoat of thenon-limiting embodiment of the opaque coating of the invention can useany of the materials of the layer of one or more metals, metal alloysand mixtures thereof, the primer layer, the dielectric layer and theprotective overcoat of the non-limiting embodiment of the coating layersdiscussed above.

Shown in FIG. 5 is another non-limiting embodiment of a coated articleof the invention designated by the number 148. In general, the coatedarticle 148 includes the coated article 30 (see FIG. 2) having an opaquelayer 146 provided over, and e.g. secured to, outer major surface 90 ofthe coated article 30. As is appreciated, the coated article 148includes the non-limited embodiments of the coated article 30 (also seeFIG. 2) having an opaque layer 146 provided over, and e.g. secured t,the surface 90 of the coating 40 of the coated article 30, The inventionis not limited to the material of the opaque coating 146, e.g. and notlimiting to the invention, the opaque layer 146 can be a coating, e.g.the non-limiting embodiments of the opaque coating 144 of the coatedarticle 42 of FIG. 3, a wood sheet, a metal sheet, an opaque plasticsheet, or opaque glass sheet, adhered, e.g. but not limiting to theinvention, by an adhesive or by lamination to the surface 90 of thecoated article 30, or a sheet transparent to visible light having anopaque coating on a surface. As can now be appreciated, the article 148is viewed through the major surface 34 of the sheet 32 of the article148.

Shown in FIG. 6 is another non-limiting embodiment of a coated articleof the invention designated by the number 154. In general, the coatedarticle 154 includes a sheet or substrate 156 having an outer majorsurface 158 and an opposite inner major surface 159. The raised portionsand/or grooves 37 are imposed in or on the inner major surface 159 ofthe sheet 156 to provide a textured surface 162. The coating 40 isprovided over, and in this particular embodiment secured to, andconforms to the textured surface 162 of the sheet 156. The sheet 156 hasa visible light transmission of 0%, i.e. the sheet 156 is opaque tovisible light. The sheet 156 can be made of any material that is opaque,e.g. and not limiting to the invention metal, wood, any type of plasticthat is opaque to visible light, e.g. and not limited to polymericmaterials, polycarbonate, acrylic and polyethylene terephthalate, andany type of glass that is opaque to visible light, or a sheet of glassor plastic transparent to visible light and having a coating to makesheet opaque to visible light, e.g. and not limited to ceramicmaterials, glass-ceramic materials, glass materials.

The raised portions and/or grooves 37 of the textured surface 159 of thesheet 156 are imposed in the surface 159 in a manner discussed above,and thereafter, the coating 40 is applied to the textured surface 162 ofthe sheet 156.

Shown in FIG. 7 is another non-limiting embodiment of a coated articleof the invention designated by the number 166. In general, the coatedarticle 166 includes a sheet or substrate 167 having an opaque layer 168provided over, and in this particular embodiment secured to, majorsurface 169 of the sheet 167. Surface 170 of the opaque layer 168 isformed with or is subsequently processed to form the scratches orgrooves and/or raised portions 37 such that the opaque layer 168 has atextured surface 172. The coating 40 is provided over, and e.g. securedto, and conforms to the abraded surface 172 of the opaque layer 168.

The sheet 167 is similar to the sheet 32 (see FIG. 2) except that thesurfaces, e.g. the surface 169 of the sheet 167, do not have thetextured surface 38 as does the surface 35 of the sheet 32. The opaquelayer 168 is not limiting to the invention and can be any opaque layersufficiently rigid to impose the grooves 37 and raised portions on thesurface 170 to provide the textured surface 172. In one non-limitingembodiment of the invention, the sheet 167 is a glass or plastic sheet,and the layer 168 is a plastic sheet adhered to the surface 169 of thesheet 167, and in another non-limiting embodiment, the sheet 167 is aglass sheet having an opaque glass frit fired onto the surface 169.Adhering glass to plastic, plastic to plastic and glass frit to glassare well known in the art and no further discussion is deemed necessary.

The grooves and/or raise portions 37 are imposed in the surface 170 ofthe opaque layer 168 in a similar manner as the grooves and/or raisedportions 37 are imposed in the surface 35 of the sheet 32. After thesurface 170 of the opaque layer 68 is textured and cleaned, the coating40 is applied to the textured surface 172 of the opaque layer 168.

In the non-limiting embodiment of the coated article 166 of theinvention shown in FIG. 7, like the non-limiting embodiment of theinvention of the coated article 154 shown in FIG. 6, the texturedsurface 172 of the article 166 shown in FIG. 7 is viewed through thecoating 40. As is appreciated, because the coated article 172 is viewedthrough the coating 40, outer surface 180 of the coated articles 154 and166 have to be protected from the environment, cleaning solution andphysical contact. The discussion of protecting the surface of the coatedarticles is presented in detail below.

EXAMPLES

Non-limiting embodiments of the present invention is illustrated by thefollowing examples. Two, 4 inch×4 inch×0.079 inch thick pieces ofStarphire® glass were cut to make the two samples. Haze measurementswere taken for each, untreated (unscratched) sample using a TCSspectrophotometer commercially available from BYK Gardner.

A surface of both samples was abraded using a ShopPro 25 Drum Sandercommercially available from Performax Products, Inc. (MN). Siliconcarbide-impregnated nylon mesh abrasive pads commercially available fromMcMaster-Carr Supply (GA). were wrapped around the cylindrical drumsander.

Each of the samples was passed through the described drum sander withthe axis of the drum sander offset at an angle of approximately 81°relative to the direction of conveyer movement. The axis of the drumsander was offset to avoid having the scratches on the surfacecontinuous from the leading edge to the trailing edge of the samples.The position of the abrasive pads was visually set to ensure uniformcontact between the abrasive pad and the surface of the samples to beabraded as the samples move passed the rotating drum sander.

The drum sander was rotated at a speed 1125 feet/minute and the speed ofthe conveyer was 5.3 feet/minute. Each sample was moved past the drumsander in the same orientation twenty times. The samples were thenwashed and dried, and the texturized or abraded surface of each samplemeasured for haze as described above. The recorded haze data is shown inTable 2 below.

TABLE 2 Haze Measurements of the Exemplary Substrates % Haze Delta %Haze Ex. 1 12.32 Unscratched 0.08 Scratched 12.40 Ex. 2 11.74Unscratched 0.06 Scratched 11.80

As can now be appreciated, in one non-limiting embodiment transparentsheets or substrates having a textured surface according to the presentinvention will have a Delta % haze of at least 10%. The inventioncontemplates texturizing the surface of the sheet to provide the sheetwith a textured surface and a Delta % haze of greater than 0%, e.g. atleast 15%, or at least 25%, or in the range of 5-50%, or in the range of5-25%, or in the range of 8-25%, depending on the desired texturedappearance of the coated article of the invention.

The invention is not limited to the optical performance of the coatedarticles or components of the coated articles of the invention, e.g. thevisible light transmission and reflection of the sheet, e.g. the sheet32, the visible light transmission and reflection of the coating, e.g.the coating 40, and the color of the coated article, e.g. the coatedarticle 30. The optical performance is selected depending on the desireduse of the coated article. By way of illustration and not limiting tothe invention, when the coated article is used as a window, the visiblelight transmission of the coated article is at least 5%, e.g. at least10%. When it is desired to use the coated article 30 as a two waymirror, one surface, e.g. the surface 35, has a higher visible lightreflectance that the opposite surface, e.g. the surface 34.

In the non-limiting embodiments of the invention discussed above, theprotective overcoat was used to protect the coating layer, e.g. thecoating 40 in FIG. 2, against deterioration. The discussion is nowdirected to other non-limiting embodiments of the invention to protectthe coating. With reference to FIG. 8, there is shown anothernon-limiting embodiment of the invention to protect the coating 40. Moreparticularly, window unit 200 includes one of the non-limitingembodiments of the coated article of the invention, e.g. but not limitedto the coated article 30, spaced from a glass sheet 202 by a spacerframe 204 to form an insulating glazing unit of a type well know in theart. The sheet 202 and coated article 30 are held together against thespacer frame 204 in any convenient manner, e.g. but not limiting toinvention by an adhesive 205 and/or a metal tape 206. The window unit200 can be used as a window for commercial and/or residential buildings,partitions for dividing large rooms or offices, and windows or doors forappliances.

In another non-limiting embodiment of the invention, the window unit 200is a window of an appliance (the appliance not shown), e.g. a window ofan oven or microwave door. The surface 90 of the coating 40 faces theexterior of the appliance and has a higher percent of visible reflectionthan the coated surface 90 facing the interior of the appliance. Thecoating 40 is preferably a transparent, low emissivity coating. Withthis arrangement, the textured surface is observed when the door of theappliance is closed and interior light 210 of the appliance turned off.The interior of the appliance can be seen with the door closed and theinterior light 210 turned on, and the heat of the appliance interior isreflected back into the appliance interior by providing that the coating40 is a low emissivity coating 40.

With reference to FIG. 9, there is shown another non-limiting embodimentof the invention to protect the coating, e.g. the coating 40. Laminatedunit 220 of FIG. 9 includes a glass or plastic sheet 222 joined to theouter surface 90 of the coated article 30 by a plastic interlayer sheet224. The laminated unit 220 shown in FIG. 9 can be a vehicular window,e.g. an automotive windshield, back window, side window, or roof window.

As can be appreciated, a coating or film 226 can be provided over one orboth of the outer surfaces of the laminated unit 220 (only shown on thesurface 34 of sheet 32 of the coated article 30 in FIG. 9), e.g. and notlimiting to the invention, a photocatalytic film or water reducing film,e.g. of the type disclosed in U.S. Pat. No. 5,873,203; U.S. Pat. No.6,027,766; and U.S. Pat. No. 6,027,766, which disclosures are herebyincorporated by reference.

It can be readily appreciated by those skilled in the art thatmodifications can be made to the invention without departing from theconcepts disclosed in the foregoing description. Such modifications areto be considered as included within the scope of the invention.Accordingly, the particular embodiments described in detail hereinaboveare illustrative only and are not limiting as to the scope of theinvention, which is to be given the full breadth of the appended claimsand any and all equivalents thereof.

1. A coating comprising: an aesthetic reflective layer selected fromsteel, copper, brass, niobium, aluminum, nichrome, tin, nickel, andchrome, noble metals and mixtures thereof; a primer layer over theaesthetic reflective layer, wherein the primer layer is selected fromthe group comprising titanium containing material, a zirconiumcontaining material, an aluminum containing material, a nickelcontaining material, a chromium containing material, a hafniumcontaining material, a copper containing material, a niobium containingmaterial, a tantalum containing material, a vanadium containingmaterial, an indium containing material, a zinc containing material, andmixtures thereof, and a dielectric layer over the primer layer, whereinthe dielectric layer is selected from the group comprising oxides oftitanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin,zinc and tin, oxides of indium-tin alloys, silicon nitrides, siliconaluminum nitrides, oxynitrides, and aluminum nitrides.
 2. The coatingaccording to claim 1, wherein the aesthetic reflective film has athickness in the range of 1 to 20 nanometers (“nm”); the primer layerhas a thickness of 1 to 10 nm; the dielectric film has a thickness inthe range of 1 to 10 nm.
 3. The coating according to claim 2, furthercomprising a protective overcoat on the dielectric layer, wherein thedielectric layer is an oxide of a mixture of silica and alumina and hasa thickness in the range of 10 to 500 nm.
 4. A heatable coating having alow emissivity, comprising: a layer of a visible light absorbingmaterial; a first dielectric layer over the layer of the visible lightabsorbing material; a first silver layer over the first dielectriclayer; a first primer layer over the first silver layer; a seconddielectric layer over the first primer layer; a second silver layer overthe second dielectric layer; a second primer layer over the secondsilver film; a third dielectric layer over the second primer layer; anda protective overcoat over the dielectric layer.
 5. The coatingaccording to claim 4, wherein the coating has color coordinatesaccording to the CIE 1976 standard with illuminant D65 at a 10° observerangle of a*=0.3, b*=4.5, and L*=78, wherein the listed color coordinatescan vary by +10%.
 6. The coating according to claim 5, wherein the layerof the visible light absorbing material is selected from titaniumnitride, nickel, chrome, and mixtures thereof and has a thickness in therange of 2 to 10 nanometers (“nm”); the first dielectric layer is on thelayer of visible light absorbing material and has a thickness in therange of 30 to 50 nm; the first silver layer is on the first dielectriclayer and has a thickness in the range of 10 to 100 nm; the first primerlayer is on the first silver layer and has a thickness in the range of 1to 6 nm; the second dielectric layer is on the first primer layer andhas a thickness in the range of 30 to 50 nm; the second silver layer ison the second dielectric layer and has a thickness in the range of 10 to100 nm; the second primer layer is on the second silver layer and has athickness in the range of 1 to 6 nm; the third dielectric layer is onthe second primer layer and has a thickness in the range of 30 to 50 nm;and the protective overcoat is on the third dielectric layer and has athickness in the range of 10 to 500 nm.
 7. A method of making an articlethat exhibits a metallic appearance comprising: treating a surface of anon-metal substrate to provide a predetermined pattern on texturedsurface of the substrate; and applying an overlay over the texturedsurface of the substrate, wherein percent visible light transmittance ofthe substrate having the overlay, and percent visible light reflectanceof the substrate having the overlay is selected such that thepredetermined pattern is visible when the article is viewed through oneof outer surfaces of the article.
 8. The method according to claim 7wherein the substrate has a Delta % haze of greater than 10%.
 9. Themethod according to claim 8, wherein the non-metal substrate is selectedfrom the group of glass and plastic, and the treating of the non-metalsubstrate is accomplished by brushing the surface of the non-metalsubstrate to impose grooves in the surface of the substrate.
 10. Themethod according to claim 7 wherein the treated surface of the non-metalsubstrate is a first surface, the non-metal substrate has a secondsurface opposite to the first surface, the overlay has a percent visibletransmission of zero, the non-metal substrate has a percent visibletransmission of greater than zero and the textured surface of thesubstrate is observed when viewed through the second surface of thesubstrate.
 11. The method according to claim 7, wherein the treatedsurface of the non-metal substrate is a first surface, the non-metalsubstrate has a second surface opposite to the first surface, theoverlay has a percent visible transmission of greater than zero, thenon-metal substrate has a percent visible transmission of greater thanzero and the textured surface of the substrate is observed when viewedthrough the first surface or the second surface of the substrate. 12.The method according to claim 11, wherein the non-metal substrate isselected from the group of glass and plastic, and the treating of thenon-metal substrate is accomplished by brushing the surface of thenon-metal substrate to impose grooves in the surface of the substrate.13. The method according to claim 7, wherein the predetermined patternhas grooves, the overlay is a coating and the applying the overlay isaccomplished by applying the coating into the grooves such that thecoating is below the surface of the non-metal substrate.
 14. The methodaccording to claim 7, wherein the predetermined pattern has grooves andridges, the overlay is a coating and the applying the overlay isaccomplished by applying the coating into the grooves such that thecoating is above the surface of the non-metal substrate and the surfaceof the non-metal substrate is completely covered.
 15. The methodaccording to claim 7, wherein treating a surface of the non-metalsubstrate is accomplished by chemically etching the surface to providegrooves in the surface.
 16. The method according to claim 7 whereintreating a surface of the non-metal substrate is accomplished bymechanical abrading the surface to provide grooves in the surface. 17.The method according to claim 16, wherein the overlay is a coating andthe applying the coating is accomplished by applying the coating tocover the surface of the non-metallic substrate, wherein the coating inthe grooves is below the surface of the non-metal substrate.
 18. Themethod according to claim 16, wherein the overlay is a coating and theapplying the coating is accomplished by applying the coating to coverthe surface of the non-metallic substrate, wherein surface of portionsof the coating in the grooves and surface of portions of the coatingoutside the grooves substantially lie in the same plane.